Lubricant compositions containing beryllium carboxylates



Patented June 20, 1950 LUBRICANT COMBO SITIONS CONTAINING :BERYL'LIUM.CARBQXYLATES John F. McGrogan,

Philadelp ia; Pa, ,assi or o The Atlantic Refining Company, Bhiladelph ia,

a corporation of Pennsylvania Noni-owin Appli n Oct b r 26,1946. SerialrNo. 706,054

The present invention relates to lubricants and particularly to mineral oil lubricantshaving incorporated therein ininorquantitiesof additive materials adapted to improve lubrication properties, and toinhibit or retard deposition of varnish, lacquer and sludge caused b deterioration of the oil in normal lubrication service. Commercial petroleum lubricating oils, no matter how highly refined, have. a definite tendency to deteriorate under the lubricating con ditions encountered-in internal combustion en,- gines. High crank case temperatures, and other increasingly severe requirements ine gine, performance, aggravate the rate of oil, deterioration from thermal decomposition and oxidation.

Claims. (mag-#3217) Deposits, in the nature of varnish, lacquer and sludge, are products of this deterioration, and in modern engines with close clearances small amounts of these deposits may seriously. inter-. iere with proper operation, ,ormay even cause engine seizure.

deterioration, and of maintaining oil cleanliness during lubrication service, are, therefore, pies; ential importance, and while the prior art sue;

gests many ways of accom lishingthese ends,

further improvement is desirable.

It is an object of this invention to provide lubricating oil compositions which are eifectively inhibited against the formation of varnish, lacquer and sludge deposits.

I. have f llndtha the bery ium s l s. o a boxylic acids of from 6 to 18 carbon atoms, and particularly of from 12 to 18 carbon atoms, are excellent detergents for all common lubricating oils, and that these compounds as additives-in small concentrations minimize .depositionofdeterioration products, and thereby improve-the over-all lubricating properties of the oil. Some of these salts are inherently soluble in petroleum oils in an amount sufiicient to provide good. detergency action, and those which are less. $91. 1.- ble can be readily'incorporated in oils withthe aid of solubilizing agents, such as aliphatic acids and alcohols, alkyl esters, or other compounds known to have a solubilizing function. The actual amount of salt additive necessary to provide the results intended may vary broadly within a range from about 0.1% to 5.0% by weight of the oil, depending upon the properties of the untreated oil base; and with the more common commercial lubricants, additions of about 0.5% to 2.0% of the beryllium salts have given very satisfactory results.

The beryllium salts which may be employed in The problems oi inhibiting oil carbon-a oms; .al sylat d n lycarboxylic aroma accordance with this invention are either the or normal .9 1 basic salts or mixtures thereofderived from 9L1? gona mixture of carboxylic acids. :Preferen e ishadpfor mo c- Or di-salts of saturated aliphatiocarboxylic, acids of from 1.2 to ,18, carblpnatqms- .iHowcve a ri of c ds may be mployed-in the pr u tion of th ery lium saltsfiineluding, oth the mono! and polycarboxyhlc acids which are exemp fi d by e n c a1 .caprvlic acid pelargonicacid, lauricacid, myristicacid, palrnitic acid, stearic acid, acids d r d rt e o dation of petroleum oils and waxe adipic acid, :n melic acid, sube c c d, az'elaic acidsebacic acid; succin c acid, and ther acidsiof that ser es in w ch. one. or. more of the me bvlen hydr aensare su i u d b un ratedh zdrocarben residues suchas olymers of e umed butvl nehavin from 8 to '18 ca be iatoms; a kylated a yl carboxy ac ds ncludinebenzcic acid .in which one Qrmore o the,;nucl .hydregen atoms. ssu-bstitut bya alkyl or. alkenyl group preferably of at ,least 6 acids such as nhthalic acid which one or more, of the nuclear hydrogenatoms is substituted by an allgyior alkenyl group of .6 or rnore .carbon atoms; abietic acid, hydrogenated abietic, acid, narlithenicac l and the e The beryllium salts of the carboxylic acids may beprepared by reacting a basic; beryllium compound, such as beryllium hydroxide or carbonate withthe oarboxylic acid at elevated temperature, the ratio of hydroxide or; carbonate to acid being such as to ive ither'a n rmalor a basic alt- ;Alternatiuely, a-soluble beryllium icompoundsuch as the chloride, nitrat or lfate in. aqueou solution, may be reacted with an aqueous solutiomondispersionof an alkali metal saltoi a c, ;bo xylic acld to give .awater-ins'oluble berylliu .carboxyla e. he nr na ationof he beryllium-salts of the carboxylic acids is ffected by conventional meanseand formsllQPfi-ltfl h present invention therei ret f rther discuss on thereof is not essential.

The beryllium salts of the carboxylic acids may be incorporated in suitable amounts in lubricating oil by simply heating the mixture until solution or dispersion is accomplished, and thereafter cooling the product to ordinary temperatures. When it is desired to increase the anti-corrosion and anti-rust properties of the lubricant, various inhibitors may be added to the oil containing the detergent beryllium carboxylates. The anti-oxidants, anti-corrosion agents, and anti-rust agents may be incorporated in amounts varying from 0.1% to 5% by weight furized esters of carboxylic acids, such as sul-' furized aliphatic abietates, sulfurized higher fatty acid esters, sulfurized sperm '1, and the like.

The present invention may be further illustrated by the following examples, which, however, are not to be construed as limiting the scope thereof:

For the detergency test, there is provideda.

glass test tube within which are vertically and concentrically disposed two sand-blasted openended steel tubes. Between the steel tubes is inserted a copper tube of small dimension through which air is delivered to the bottom of the test tube .belowthe end of the inner steel tube. In carrying out' the test, the inner steel tube is weighed and then inserted in the testing apparatus. '15 cc. of the oil to be tested is then introduced into the glass test tube and forms a pool covering the lower ends of the steel tubes and the copper tube. The apparatus is then placed in an oil bath and heated to 300 F., air being injected through the copper tube and beneath the surface of the test oil at a rate of 30 liters per hour. After 65 hours heating and blowing, the apparatus is removed from the oil bath and cooled. The inner steel tube is withdrawn, washed with naphtha, and weighed, the increase in weight being attributed to the deposition of sludge. The smaller the weight increase, the more efiective the'detergent agent in the oil. The results of the tests are tab ulated below. The base lubricating oil used was a raflinate fraction of a nitrobenzene selective solvent extracted distillate lubricating stock, such base oil having an A. P. I. gravity of 31 and a Saybolt Universal viscosity of 175 seconds at Milligrams Lubricant sludge deposited Base oil 63 Base oil+0.5% beryllium mono-stearate. 13 Base oil+l.0% beryllium mouo-stearate.- 3 Base oil+2.0% beryllium mono-srearate *3 Base oil+l.0% beryllium di-stearate.-- 0 Base oil+2.0% beryllium di-stearate 1 While, in the above test, a solvent refined lubricating oil was employed as the base, other hydrocarbon oils may be used in lieu thereof, including straight-run lubricating distillates from paraffin base, naphthene base, or mixed base crude oils, acid treated oils, hydrogenated oils, clay treated mass;

hydrocarbon oil 4 oils, deasphaltized residual oils, and synthetic oils produced by the polymerization of olefins or the condensation of olefins or halogenated hydrocarbons with aromatic hydrocarbons.

I claim:

1; A lubricating oil composition comprising hydrocarbon oil and a beryllium salt of a carboxylic acid containing from 6 to 18 carbon atoms, said salt being present in an amount suificient to improve the detergency of the oil when used in the lubrication of internal combustion engines.

2. A lubricating oil composition comprising hydrocarbon oil and from 0.1% to 5% by weight of a beryllium salt of a carboxylic acid containing from 6 to 18 carbon atoms. 3. A lubricating oil composition comprising and from 0.5% to 2% by weight of a beryllium salt of a carboxylic acid containing from 6 to 18 carbon atoms.

4. A lubricating oil composition comprising hydrocarbon oil and from 0.1% to 5% by weight of a beryllium salt of a saturated aliphatic carboxylic acid containing from 6 to 18 carbon atoms.

5. A lubricating oil composition comprising hydrocarbon oil and from 0.5% to 2% by weight of beryllium stearate.

6. A lubricating oil composition comprising hydrocarbon oil and from 0.5% to 2% by weight of beryllium mono-stearate.

7. A lubricating oil composition comprising hydrocarbon oil and from 0.5% to 2% by weight of beryllium di-stearate.

8. A lubricating oil composition comprising hydrocarbon oil, 0.5% to 2% by weight of beryllium stearate, and 0.5% to 2% of a metal salt of an acid ester of an acid of phosphorus.

9. A lubricating oil composition comprising hydrocarbon oil, 0.5% to' 2% by weight of beryllium stearate, 0.5% to 2% of a metal salt of an acid ester of an acid of phosphorus, and 0.5% to 2% of sulfurized ester of a carboxylic acid.

10. A lubricating oil composition comprising hydrocarbon oil, 0.5% to 2% by weight of beryllium stearate, 0.5% to 2% by weight of a metal salt of an acid thiophosphate, and 0.5% to 2% by weight of sulfurized sperm oil.

JOHN F. MCGROGAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,320,392 White June 1, 1943 2,322,307 Neely June 22, 1943 CTHER REFERENCES 

1. A LUBRICATING OIL COMPOSITION COMPRISING HYDROCARBON OIL AND A BERYLIUM SALT OF A CARBOXYLIC ACID CONTINING FROM 6 TO 18 CARBON ATOMS, SAID SALT BEING PRESENT IN AN AMOUNT SUFFICIENT TO IMPROVE THE DETERGENCY OF THE OIL WHEN USED IN THE LUBRICATION OF INTERNAL COMBUSTION ENGINES. 